A chromate-contaminated site in southern Switzerland – Part 1: Site characterization and the use of Cr isotopes to delineate fate and transport

The risk of groundwater contamination by chromate at a former chromite ore processing industrial site in Rivera (Switzerland) was assessed by determining subsoil Cr(VI) concentrations and tracking naturally occurring Cr(VI) reduction with Cr isotopes. Using a hot alkaline extraction procedure, a total Cr(VI) contamination of several 1000 kg was estimated. Jarosite, KFe₃((SO₄)_x(CrO₄)_1−x)₂(OH)₆, and chromatite (CaCrO₄) were identified as Cr(VI) bearing mineral phases using XRD, both limiting groundwater Cr(VI) concentrations. To track assumed Cr(VI) reduction at field scale δ⁵³Cr values of contaminated subsoil samples in addition to groundwater δ⁵³Cr data are used for the first time. The measurements showed a fractionation of groundwater δ⁵³Cr values towards positive values and subsoil δ⁵³Cr towards negative values confirming reduction of soluble Cr(VI) to insoluble Cr(III). Using a Rayleigh fractionation model, a current Cr(VI) reduction efficiency of approximately 31% along a 120 m long flow path was estimated at an average linear groundwater velocity of 3.3 m/d. Groundwater and subsoil δ⁵³Cr values were compared with a site specific Rayleigh fractionation model proposing that subsoil δ⁵³Cr values can possibly be used to track previous higher Cr(VI) reduction efficiency during the period of industrial activity. The findings strongly favor monitored natural attenuation to be part of the required site remediation measures.     

Variations of sea surface temperature and primary productivity during Heinrich and Dansgaard-Oeschger events in the northeastern Arabian Sea

Sea surface temperatures (SST) and primary productivities have been reconstructed for the northeastern Arabian Sea during the past 65,000 years, using C₃₇-alkenones. Comparison of this SST record with '¹⁸O from Greenland ice core GISP2 shows striking similarities, indicating an apparent linkage between the climate of the Arabian Sea with that of the northern North Atlantic, most probably via atmospheric and/or oceanic circulation. These rapid SST changes are in the long term overlain by insolation changes at 30°N.     

Leveraging correlation across space and time to interpolate geophysical data via CoKriging

Managing geophysical data generated by emerging spatiotemporal data sources (e.g. geosensor networks) presents a growing challenge to Geographic Information System science. The presence of correlation poses difficulties with respect to traditional spatial data analysis. This paper describes a novel spatiotemporal analytical scheme that allows us to yield a characterization of correlation in geophysical data along the spatial and temporal dimensions. We resort to a multivariate statistical model, namely CoKriging, in order to derive accurate spatiotemporal interpolation models. These predict unknown data by utilizing not only their own geosensor values at the same time, but also information from near past data. We use a window-based computation methodology that leverages the power of temporal correlation in a spatial modeling phase. This is done by also fitting the computed interpolation model to data which may change over time. In an assessment, using various geophysical data sets, we show that the presented algorithm is often able to deal with both spatial and temporal correlations. This helps to gain accuracy during the interpolation phase, compared to spatial and spatiotemporal competitors. Specifically, we evaluate the efficacy of the interpolation phase by using established machine-learning metrics (i.e. root mean squared error, Akaike information criterion and computation time).     

New insights into Late Pleistocene glacial and postglacial history of northernmost Ungava (Canada) from Pingualuit Crater Lake sediments

The Pingualuit Crater was formed by a meteoritic impact ca. 1.4 million years ago in northernmost Ungava (Canada). Due to its geographical position near the center of successive North American ice sheets and its favorable morphometry, the Pingualuit Crater Lake (water depth = 246 m) promises to yield a unique continuous sedimentary sequence covering several glacial/interglacial cycles in the terrestrial Canadian Arctic. In this paper, we suggest the existence of a subglacial lake at least during the Last Glacial Maximum (LGM) by hydraulic potential modeling using LGM ice-surface elevation and bed topography derived from a digital elevation model. These results support the hypothesis that the bottom sediments of the Crater Lake escaped glacial erosion and may contain a long-term continental sedimentary sequence. We also present the stratigraphy of a 9 m-long core retrieved from the deep basin of the lake as well as a multiproxy reconstruction of its deglacial and postglacial history. The base of the core is formed by very dense diamicton reflecting basal melt-out environments marking the end of subglacial conditions at the coring site. The overlying finely laminated silt are related to the onset of proglacial conditions characterized by extremely low lacustrine productivity. Infra Red Stimulated Luminescence and AMS ¹⁴C dating, as well as biostratigraphic data indicate sediment mixing between recent (e.g. Holocene) and much older (pre- to mid-Wisconsinan) material reworked by glacier activity. This process prevents the precise dating of these sediments that we interpret as being deposited just before the final deglaciation of the lake. Two finer grained and organic-rich intervals reflect the inception of lacustrine productivity resulting from the cessation of glacial meltwater inputs and ice-free periods. The lower organic interval corresponds to the early postglacial period (6850–5750 cal BP) and marks the transition between proglacial and postglacial conditions during the Holocene Thermal Maximum, while the uppermost organic-rich core section represents late Holocene sediments (～4200–600 cal BP). The organic intervals are separated by a basin-scale erosive slide occurring around 4200 cal BP and likely related to 1) a seismic event due to the glacio-isostatic rebound following the last deglaciation or 2) slope instabilities associated with rapid discharge events of the lake.     

No significant ice-sheet expansion beyond present ice margins during the past 4500 yr at Rauer Group, East Antarctica

The history of glacial advances and retreats of the East Antarctic ice sheet during the Holocene is not well-known, due to limited field evidence in both the marine and terrestrial realm. A 257-cm-long sediment core was recovered from a marine inlet in the Rauer Group, East Antarctica, 1.8 km in front of the present ice-sheet margin. Radiocarbon dating and lithological characteristics reveal that the core comprises a complete marine record since 4500 yr. A significant ice-sheet expansion beyond present ice margins therefore did not occur during this period.     

Comparison of Large-Eddy Simulation Data with Spatially Averaged Measurements Obtained by Acoustic Tomography – Presuppositions and First Results

An attempt is made to compare results oflarge-eddy simulation (LES) in a convective boundarylayer using the model PALM with experimental data obtained from acoustic travel time tomography.This method provides two-dimensional data arrays, which are considered as more suitable forLES-validation than classical local orline-integrated measurements, because the tomographic data are area- or volume-averaged.For a quantitative comparison with experimental data in general, some prerequisites have to be considered: First of all, the initial and boundary conditions of the LES model have to be provided correctly by the experiment. Considering measurement errors, a sensitivity study was performed to investigate the influence of inaccurate initial and boundary conditions on the simulation results.This showed that for determining some boundary conditions, such as the surface temperature and the roughness length, high measurement accuracies are necessary, which are difficult to reach or which at least require considerable extra measurement efforts.The initial and boundary conditions provided by the Lindenberg experiment in 1999 turned out to be of insufficient accuracy to allow quantitative comparisons.However, a qualitative comparison was performed instead to investigate if the acoustic tomography method is a proper method for comparisons with LES models in general.It showed a good qualitative agreement with some quantitative differences. These differences can partly be explained by the sensitivity of the LES to initial and boundary conditions and by the limitations of the acoustic tomography.     

The peat bog at Zinnwald-Georgenfeld revisited after 25 years: Geochemical investigation of water,Sphagnum moss and peat cores

From 1992 to 1994, trace metal concentrations of bog water, Sphagnum mosses and peat cores of the bog “Georgenfelder Hochmoor” at Zinnwald-Georgenfeld in the Eastern Ore Mountains (Germany) were investigated. A sampling campaign in September 2019 allows the comparison of the older measurements with today's trace metal concentrations. No changes were found in the bog waters, while the trace metal concentrations of the Sphagnum mosses have decreased significantly. Due to the low growth rate of the peat and despite certain heterogeneity between the peat cores, the investigated elemental data for the peat sampled in the 1990s and in 2019 are in the same concentration range. The maximum concentrations are measured in the upper samples of all peat cores for the analysed elements (except sulphur). Compared to upper crustal data, a different behaviour of the elements is observed: Cr, Sc, Ti, and V, rare earth elements show crustal ratios, while Al and Si are also influenced by crust-air fractionation. Cd, Cu, Ni, Pb, and Zn are additionally enriched by anthropogenic atmospheric inputs from industry and transport. These results confirm the assumption that peat cores record past atmospheric deposition.     

High-resolution methane profiles across anoxic brine–seawater boundaries in the Atlantis-II, Discovery, and Kebrit Deeps (Red Sea)

A decrease in temperature (ΔT up to 45.5 °C) and chloride concentration (ΔCl up to 4.65 mol/l) characterises the brine–seawater boundary in the Atlantis-II, Discovery, and Kebrit Deeps of the Red Sea, where redox conditions change from anoxic to oxic over a boundary layer several meters thick. High-resolution (100 cm) profiles of the methane concentration, stable carbon isotope ratio of methane, and redox-sensitive tracers (O₂, Mn⁴⁺/Mn²⁺, Fe³⁺/Fe²⁺, and SO₄²⁻) were measured across the brine–seawater boundary layer to investigate methane fluxes and secondary methane oxidation processes.

Substantial amounts of thermogenic hydrocarbons are found in the deep brines (mostly methane, with a maximum concentration up to 4.8×10⁵ nmol/l), and steep methane concentration gradients mainly controlled by diffusive flow characterize the brine–seawater boundary (maximum of 2×10⁵ nmol/l/m in Kebrit Deep). However, locally the actual methane concentration profiles deviate from theoretical diffusion-controlled concentration profiles and extremely positive δ¹³C–CH₄ values can be found (up to +49‰ PDB in the Discovery Deep). Both, the actual CH₄ concentration profiles and the carbon-13 enrichment in the residual CH₄ of the Atlantis-II and Discovery Deeps indicate consumption (oxidation) of ¹²C-rich CH₄ under suboxic conditions (probably utilizing readily available—up to 2000 μmol/l—Mn(IV)-oxihydroxides as electron acceptor). Thus, a combined diffusion–oxidation model was used to calculate methane fluxes of 0.3–393 kg/year across the brine–seawater boundary layer. Assuming steady-state conditions, this slow loss of methane from the brines into the Red Sea bottom water reflects a low thermogenic hydrocarbon input into the deep brines.     

1996-2015年纽约湾区生态系统服务对景观格局变化的响应

生态系统服务价值对景观格局演变的响应研究已成为地理学、生态学等领域的研究热点。以纽约湾区为研究区,利用1996—2015年土地覆被数据和数字高程数据,采用生态系统服务价值当量估算法、景观格局指数、空间自相关分析等方法,分析1996—2015年湾区景观格局的时空演变规律,定量评估研究区生态系统服务价值,探讨纽约湾区生态系统服务价值对景观格局变化的响应。结果表明：①纽约湾区景观以林地和建设用地为主,其整体变化幅度较小,20年间湿地面积减少约10.94%,而建设用地增长幅度较高,约25.91%。②纽约湾区1996—2015年间ESV总量呈逐步减少,20年间共减少57.83亿元,2000—2005年间下降幅度较大约1.69%。③湾区ESV空间异质性较强,不同地区ESV增减所对应的土地利用转移各有差异。湾区南部热点区多出现湿地增加,而北部则以水域、草地增加为主。湾区西部冷点区多为湿地转林地的现象,而中部冷点区则以建设用地增加为主。④除建设用地外,湾区其余地类均呈现人为干预越少,景观结合度、聚集度越高,越有利于提升湾区整体的生态系统服务价值的规律。⑤纽约湾区ESV强度与土地利用程度（La）的空间关联性较弱,且湾区生态环境质量逐年下降。研究结果希望对世界级大湾区环境资源利用率的提升研究具有借鉴意义。